Dimethylsulfonium - 2-((alkoxycarbonyl)carbonyl)phenacylides and derivatives thereof

ABSTRACT

DIALKYL SULFONIUM A-(ALKOXYCARBONYLCARBONYL)PHENACYLIDES, USEFUL AS FUNGICIDES.

United States Patent 3,739,012 DIMETHYLSULFONIUM 2-[(ALKOXYCARBONYL) CARBON YL]PHENACYLIDES AND DERIVATIVES THEREOF Kenneth Wayne Ratts, 12139 Lake Como Drive, Creve Coeur, Mo. 63141 No Drawing. Continuation of application Ser. No.

765,733, Aug. 8, 1968, which is a division of application Ser. No. 549,160, May 11, 1966, both now abandoned. This application Feb. 16 1971, Ser.

Int. (:1. C070. 149/46 US. Cl. 260470 3 Claims ABSTRACT OF THE DISCLOSURE Dialkyl sulfonium a-(alkoxycarbonylcarbonyl)phenacylides, useful as fungicides.

ROE: Y O

Rog R wherein R and R are each selected from the group consisting of hydrogen, alkyl of not more than 12 carbon atoms and haloalkyl of not more than 12 carbon atoms containing 1, 2 or 3 halogen atoms (Cl, Br, F and I), R is selected from the group consisting of halogen (Cl, Br, F and I) and alkyl of not more than 4 carbon atoms, R is selected from the group consisting of N0 and alkoxy of not more than 4 carbon atoms, R is phenyl, a is an integer from 0 to 5 inclusive, b is an integer from 0 to 2 inclusive, c is an integer from 0 to 1, and Y is selected from the group consisting of 0 O O O O 0 (a) -iiiiru, (b) Allow, (a iJN and R n R 11,

wherein R is alkyl of not more than 4 carbon atoms, R and R are each selected from the group consisting of alkyl of not more than 4 carbon atoms, alkenyl of not more than 4 carbon atoms and phenyl, X and X are halogen (Cl, Br, F and I) and s and t are integers from 0 to 5 inclusive, R is selected from the group consisting of alkyl of not more than 4 carbon atoms and halogen (Cl, Br, F and I), 'R is N0 n is an integer from 0 to 3 inclusive and m. is an integer from 0 to 2 inclusive.

In the above formula the alkyl of R and R can be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, secbutyl, isobutyl, tert-butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl and the various homologues and isomers of alkyl having from 1 to 12 carbon atoms, and the haloalkyl of R and R can be, for example, chloromethyl, iodomethyl, bromomethyl, fluoromethyl, trichloromethyl, tribromomethyl, chloroethyl, iodoethyl, bromoethyl, iiuoroethyl, dichloroethyl, chloro-n-propyl,

Bi -x e bromo-n-propyl, iodoisopropyl, bromo-n-butyl, bromotert-butyl, 1,3,3-trichlorobutyl, 1,3,3-tribromobutyl, chloropentyl, bromopentyl, 2,3-dichloropentyl, 3,3-dibromopentyl, chlorohexyl, bromohexyl, 2,4-dichlorohexyl, 1,3- dibromohexyl, 1,3,4-trichlorohexyl, chloroheptyl, bromoheptyl, fluoroheptyl, 1,3-dichloroheptyl, 1,4,4-trichloroheptyl, 2,4-dichloromethylheptyl, chlorooctyl, bromooctyl, iodooctyl, 2,4-dichloromethylhexy1, 2,4-dichlorooctyl, 2, 4,4-trichloromethylpentyl, 1,3,5-tribromooctyl and the halogenated straight and branched chain nonyl, decyl, undecyl and dodecyl.

As alkyl, R R R R and R each can be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl. As alkoxy, R can be methoxy, ethoxy, npropoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, and tert-butoxy.

The a-substituted sulfonium ylids of this invention are prepared by a process which comprises reacting a sulfonium ylid of the formula ROE: O

RICH: R2,, R

with a compound selected from the group consisting of o o a xii-dz and (B) @NCO wherein Z is as defined above.

The process utilizing reactant (A) is carried out by reacting substantially 2 molar equivalents of sulfonium ylid with one molar equivalent of the substituted-carbonyl chloride compound in the presence of an inert organic medium at a temperature in the range of about 0 C. to about 60 C. However, higher or lower temperatures can be used, the temperature not being critical. Pressure is likewise not a critical factor in the process of this invention employing reactant (A). Pressure both above and below atmospheric pressure can be employed, although atmospheric pressure is preferred for convenience.

Illustrative substituted-carbonyl chloride compounds useful in the preparation of the sulfonium ylids of this invention include:

methoxalyl chloride ethoxalyl chloride propoxalyl chloride sec-butoxalyl chloride (methylcarbonyl) carbonyl chloride (ethylcarbonyl)carbonyl chloride (isopropylcarbonyl)carbonyl chloride (sec-'butylcarbonyl)carbonyl chloride (tert-butylcarbonyl)carbonyl chloride N,N-dimethylcarbamoylcarbonyl chloride N,N-diethylcarbamoylcarbonyl chloride N,N-dibutylcarbamoylcarbonyl chloride N,N-di(tert-butyl)carbamoylcarbonyl chloride N,N-dichloromethylcarbamoylcarbonyl chloride N,N-di(2-chloroethyl)carbamoylcarbonyl chloride N,N-di(2-chlorobutyl)carbamoylcarbonyl chloride N,N-di(2-fluoropropyl)carbamoylcarbonyl chloride N-methyl-N-ethylcarbamoylcarbonyl chloride N,N-divinylcarbamoylcarbonyl chloride N,N-diallylcarbamoylcarbonyl chloride N,N-di(2-'buten-1-yl)carbamoylcarbonyl chloride N,N-di(2-bromopropen-1-yl)carbamoylcarbonyl chloride N,N-diphenylcarbamoylcarbonyl chloride When reactant (B) above is used the process can be represented by the following representative synthesis:

The process utilizing reactant (B) is preferably carried out with substantially equimolar amounts of reactants, although a small excess of either can be used, in the presence of an inert organic medium. Reaction temperature and pressure are not critical and temperatures and pressures disclosed above for the process utilizing reactant (A) are suitable.

Illustrative isocyanates useful in the preparation of the sulfonium ylids of this invention include:

phenyl isocyanate 2,4-dimethylphenyl isocyanate 2,4,6-trirnethylphenyl isocyanate 3,5-dimethylphenyl isocyanate 4-methylphenyl isocyanate 4-tert-butylphenyl isocyanate 3,5-diethylphenyl isocyanate 2-methylphenyl isocyanate 6-methylphenyl isocyanate 6-tert butylpheny1 isocyanate 3,5-di-n-propylphenyl isocyanate 2,6-dimethylphenyl isocyanate 2-methyl-6-nitrophenyl isocyanate 4-chlorophenyl isocyanate 2,4-dichlorophenyl isocyanate 2,4,6-trichlorophenyl isocyanate 2,4,6-tribromophenyl isocyanate 3,5-diiodophenyl isocyanate 2,6-difluorophenyl isocyanate 3,5-dichlorophenyl isocyanate 2,6-dichlorophenyl isocyanate 2-chlorophenyl isocyanate 4-bromophenyl isocyanate 2,6-dibromophenyl isocyanate 2-chloro-4-nitrophenyl isocyanate 4-nitrophenyl isocyanate 6-nitrophenyl isocyanate 2,4-dinitrophenyl isocyanate 2,6-dinitrophenyl isocyanate 3,5-dinitrophenyl isocyanate Inert organic media which can be used in the process of this invention utilizing either reactant (A) or reactant (B) include, for example, hydrocarbons such as benzene, toluene, xylene, cyclohexane, methylcyclohexane, n-heptane, n-hexane and the like and organic halides such as carbon tetrachloride, n-butylchloride, ethylenedichloride, chlorobenzene and the like.

The separation of the resulting reaction product from the reaction mixture is readily accomplished. The solvent can be removed by stripping or distillation, preferably low temperature vacuum distillation. The product if desired can be purified by any of the conventional means well-known in the art, selective extraction, recrystallization or any suitable combination of these methods.

The OL-SUbStltlltCd sulfonium ylids of this invention are crystalline solid materials which are insoluble in Water but somewhat soluble in many organic solvents, for example alcohols, ketones, hydrocarbons such as benzene, toluene, xylene and the like and chlorohydrocarbons such as chlorobenzene carbon tetrachloride and the like.

The sulfonium ylids used as starting materials in the preparation of the tit-substituted sulfonium ylids of the invention are prepared by reacting a sulfonium salt of the formula s-omo with a substantially equimolar amount of an alkaline material such as sodium hydride in the presence of an inert liquid medium such as tetrahydroufuran, where R, R R R R a, b, c and X as defined above.

The following examples illustrate the invention. Parts and percent are by weight unless otherwise indicated.

EXAMPLE 1 A suitable reaction vessel is charged with a solution of 4.5 parts of dimethylsulfonium 4-nitrophenacylide in 70 ml. of methylene chloride and then a solution of 4.7 parts of 3,4-dichlorophenyl isocyanate in methylene chloride is added dropwise over a period of a few minutes. The reaction mixture is filtered to recover the solids which are crystallized from methylene chloride to give 6.9 parts of dimethylsulfonium-2-[(3',4'-dichlorophenyl) carbamoyl]-4'-nitrophenacylide, M.P. 223-229 C. The product is confirmed by infrared spectrum analysis.

Calcd for C H Cl N O S (percent): C, 49.40; H, 3.41; Cl, 17.16; N, 6.78; O, 15.49; S, 7.76. Found (percent): C, 49.65; H, 3.65; Cl, 16.89; N, 6.77; O, 15.31; S, 7.73.

EXAMPLE 2 A suitable reaction vessel is charged with about 4.5 parts of dimethylsulfonium 4'-nitrophenacylide, 50 parts of benzene and 10 parts of methylene chloride. A solution of about 1.4 parts of ethoxalyl chloride in 15 parts methyl alcohol is then added dropwise to the reaction vessel over a 5 minute period with stirring at about 50 C. The reaction mixture is filtered to remove the solids (3.8 parts) which are then extracted with benzene. The benzene extract is concentrated under vacuum to give 1.0 part of yellow solid. The filtrate from the reaction mixture is concentrated under vacuum to give 1 part of an orange solid. The orange solid and yellow solid are combined and recrystallized twice from benzene to give 1.5 parts of dimethylsulfonium 2 [(ethoxycarbonyl)carbonyl]-4'- nitrophenacylide, M.P. 164-1645 C.

Calcd for C H NO S (percent): C, 61.68; H, 4.65; N, 4.31; S, 9.86. Found (percent): C, 52.15; H, 4.51; N, 4.87; S, 9.99.

Following substantially the same procedure as in the foregoing examples the following compounds of this invention are prepared.

Example:

3 Dimethylsulfonium-Z-(phenylcarbamoyl) phenacylide 4 Dimethylsulfonium-2- (3',5-dibromophenyl) carbamoyl) -4-chlorophenacylide 5 Dimethylsulfonium-2-(4-iodophenylcarbamoyl)- 4-methoxyphenacylide 6 Dimethylsulfonium-Z-(4-methylphenylcarbamoyl -2',4'-dimethoxyphenacylide T Dimethylsulfonium-Z-[-(2,-4-dimethylphenyl)carbamoyl] -4-phenylphenacylide 8 Dimethylsulfonium-Z-[(2',4,'6-trimethylphenyl) carbamoyl] -4-phenacylide 9 Dimethylsulfonium-Z- (p-ethylphenylcarbamoyl 2',4-dichlorophenacylide 10 Dimethylsulfonium-Z(m-methylphenylcarbamoyl -2',4-dibromophenacylide 1 1 Dimethylsulfonium-2- (m-tert-butylphenylcarbamoyl) -2',4'-dimethylphenacylide 12 Dimethylsulfonium-Z- 2',6'-di (tert-butyl)phenylcarbamoyl] -2'-methylphenacylide l3 Dimethylsulfonium-2-(m-fluorophenylcarbamoyl) -4'-methylphenacylide l4 Dimethylsulfonium-2- (2',4'-dinitrophenyl) carbamoyl] -4-ethylphenacylide 1 5 Dimethylsulfonium-Z- p-nitrophenylcarb amoyl phenacylide 16 Dimethylsulfonium-2-[ (2'-methyl-4-nitrophenyl) carb amoyl] phenacylide '1 7 Dimeth'ylsulfonium-2- [2'- chloro-4'-nitrophenyl) carbamoyl] -4'-methylphenylacy1ide l 8 Dimethylsulfonium-Z-[2',4', 6'-trichlorophenyl) carb amoyl] phenacylide 19 Dimethylsulfoninm-2- (N,N-dimethylcarbamoyl) carbonyl] -2',4'-diethoxyphenylacylide 20 Dimethylsulfonium-Z- (N,N-diethylcarbamoyl) carbonyl] -2',4'-dichlorophenylacylide 21 Dimethylsulfonium-2[ (N,N-divinylcarbamoyl) carbonyl] phenacylide 22 Dimethylsulfonium-2- (N,N-dipropenylcarbamoyl) carbonyl] -4-methylphenylacylide 23 Dimethylsulfonium-Z- [N,N-di (chloromethyl) carbamoyl] phenacylide 24 Dimethylsulfonium-2-[ (N, N-di-2- chlorobutylcarbamoyl carbonyl] -2',4'-dichlorophenylacylide 25 Dimethylsulfonium-2- (N,N-di-3-chlorobuten-1- ylcarb amoyl) carbonyl] phenacylide 26 Dimethylsulfonium-2-[ (N,N-diphenylcarbamoyl carbonyl] phenacylide 27 Dimethylsulfonium-2- (N,N-di [2',4'-dich1orophenyl] carbamoyl -carbonyl] phenacylide 28 Dimethylsulfonium-2-[ (N,N-di [2',4',6-tr ibromophenyl] carbamoyl) -carbonyl[phenacyhde 29 Dimethylsulfonium-Z- (N,N-di [p-fluorophenyl] carbamoyl) carbonyl] phenacylide 30 Dimethylsulfonium2-[ (methoxycarbonyl) carbonyl] phenacyclide 3 1 Dimethylsulfonium-2- ethoxycarbonyl) carbonyl] -4-methylphenacylide 32 Dimethylsulfonium-Z- (propoxycarbonyl)carbonyl]-2',4'-dichlorophenacylide 33 Dimethylsulfonium-Z- (methylcarbonyl) carbonyl] -4'-nitrophenacylide '34 Dimethylsulfonium-Z- [(n-butylcarbonyl) carbonyl] -4'-methoxyphenacylide 35 Diethylsulfonium-2- (methoxycarbonyl) carbonyl] -2'-tert-butylphenacylide 3 6 Diamylsulfonium-Z- 2',4'-dimethylpheny1) carbamoyl] -2',4',6'-trichlorophenacylide 37 Di (2-chloroethyl) sulfonium-2- (propylcarbonyl) carbonyl] phenacylide 3 8 Methylethylsulfonium-Z- ethoxycarbonyl) carbonyl]-2',4', -trimethylphenacylide 6 3 9 Dimethylsulfonium-2- (3 ',4'-dichlorophenyl carbamoyl]-2,4'-dichlorophenacylide 40 Dimethylsulfonium-2 (N,N-dimethylcarbamoyl) carbonyl] -4-tert-butylphenacylide The tat-substituted sulfonium ylids of this invention are useful as pesticides, particularly fungicides. In practicing the fungicidal methods of this invention, one or more of the present Ot-SllbStitlltfid sulfonium ylids is applied to the fungal organisms or the material to be treated for the control of fungi in an amount of sufiicient to exert fungicidal activity. The fungicidal ylids of this invention are particularly effective when applied directly to the soil for control of soil borne fungal organisms. They are also effective in the treatment of plant life such as vegetables, ornamental plants and fruit-bearing trees; organic fibers and fabrics; leather; paints and lubricating oils and various cellullosic materials such as Wood. In application to soil and plants, fungicidal control is obtained in most instances by the application of about 0.01 pound to about 25 pounds of active ingredient per acre. The preferred amount is determined by and dependent upon the particular fungicidal ylid selected, the method of application, and in the case of application to plant life, the state and condition of growth and the climatic conditions.

The effectiveness of the compounds of this invention as fungicides is illustrated below.

Slide germination test: The concentration of active ingredient required to substantially inhibit germination of spores from 7- to 10-day-old cultures of Venturia inaequalis is determined by the slide germination test. A concentrated formulation of 1.0 gram of dimethylsulfonium- 2-[(ethoxycarbonyl)carbonyl] 4' nitrophenacylide, acetone and 0.1 gram of sorbitan monolaurate polyoxyethylene derivative (a commercial water-soluble non-ionic emulsifying agent) is prepared. This concentrated formulation is diluted with sufficient Water to provide an aqueous emulsion containing 10 p.p.m. of the nitrophenacylide. To a test tube is then added four volumes of the aqueous emulsion, one volume of spore stimulant and one volume of spore suspension, the spore stimulant being added to insure a high and relatively stable percentage of germination of the control. Drops of the test specimen mixture and an untreated control are pipetted onto glas slides. The glass slides are then placed in moist chambers for 20 hours incubation at 22 C. Germination counts are made by counting potentially viable spores, i.e. spores which would germinate under the normal conditions of the control. It was found that the fungicidal nitrophenacylide substantially inhibited germination of the spores Whereas the control spores completely germinated.

In a similar evaluation against the late blight fungus Phytophthora infestans at a concentration of 10 p.p.m., dimethylsulfonium 2 [(ethoxycarbonyl)carbonyl] 4- m'trophenacylide substantially prevented germination of spores of said fungus.

The fungicidal compositions of this invention contain at least one active ingredient and a material referred to in the art as a fungicidal adjuvant in liquid or solid form. The fungicidal compositions are prepared by admixing the active ingredient with an adjuvant including diluents, extenders, carriers and conditioning agents to provide compositions in the form of finely-divided particulate solids, granules, pellets, aerosols, solutions, dispersions or emulsions. Thus the active ingredient can be used with an adjuvant such as a finely-divided particulate solid, a liquid of organic origin, water, a wetting agent, dispersing agent, 81111 emulsifying agent or any suitable combination of t ese.

Typical finely-divided solid carriers and extenders which can be used in the fungicidal compositions of this invention include for example, the tales, clays, pumice, silica, diatomaceous earth, quartz, Fullers earth, salt, sulfur, powdered cork, cottonseed hulls, powdered wood, walnut flour, chalk, charcoal, tobacco dust, volcanic ash, wheat flour, soybean flour, tripoli, redwood flour, and the like.

Typical liquid diluents include for example, water, kerosene, Stoddard solvent, hexane, benzene, toluene, acetone, ethylene dichloride, xylene, alcohols, Diesel oil glycols and the like. Typical diluents for aerosols include for example, Freons such as dichlorodifluoromethane, trichlorofluoromethane, and the like.

The fungicidal compositions of this invention particularly liquids and wettable particles, usually contain as a conditioning agent one or more surface-active agents in amounts sufficient to render a given composition readily dispersible in Water or in oil. By the term surface-active agen it is understood that wetting-agents, dispersing agents, suspending agents, emulsifying agents and the like are included therein.

The surface-active agents employed can be of the anionic, cationic or nonionic type. They include, for example, sodium oleate, sulfonated petroleum oils, alkyl aryl sulfonates, sodium lauryl sulfate, polyethylene oxides, lignin sulfonates, and other surface-active agents.

The fungicidal compositions of this invention generally contain from about 0.005% to about 95% by weight of the active fungicdal ingredient.

The active compounds of the present invention can be employed in combination with other fungicides to give compositions that have broad spectrum fungicidal activity. In these mixtures, the auxiliary fungicidally active materials can be present in any desired amount, ordinarily from about 0.1 to about 20 parts by weight per one part by weight of tat-substituted sulfonium ylid of the present invention. In some instances it may even be desirable to employ two or more auxiliary fungicides.

Typical of the auxiliary fungicides that can be employed in combination with the tat-substituted sulfonium ylids of the present invention are the following:

N-trichloro-methylthio-4-cyclohexene-1,2dicarboximide Tetramethylthiuram disulfide Manganese ethylene-bis-dithiocarbamate Ferric dimethyl dithiocarbamate Zinc ethylene-bis-dithiocarbamate Zinc dimethyl dithiocarbamate Tetra copper calcium oxychloride Tetrachloro-p-benzoquinone 2,3-dichloro-1,4-naphthoquinone 2-dichloro-6- (o-chloroanilino) triazine Ethylene thiuram monosulfide 2-heptadecy1 glyoxalidine acetate Ferric dimethy dithiocarbamate plus 2-mercaptobenzothiazole Manganese dimethyl dithiocarbamate plus 2-mercaptobenzothiazole Copper dihydrazinium sulfate Copper-S-quinolinolate Cycloheximide Terramycin Streptomycin When operating in accordance with the present invention, the a-substituted sulfonium ylids or a composition containing them can be applied to the fungal organisms to be controlled, or to their habitats in any convenient fashion, e.g. by means of hand clusters or sprayers. Applications to the above-ground portions of plants conveniently can be carried out With powder dusters, boom sprayers and spray dusters. In foliar applications, the employed compositions should not contain any appreciable amount of phytotoxic diluents. In large scale operations, dusts or low volume sprays can be applied from airplanes.

The term fungicidal composition as used herein and in the appended claims is intended to mean not only compositions in a suitable form for application but also concentrated compositions which require dilution or extension with a suitable quantity of liquid or solid adjuvant prior to application.

Although the invention is described with respect to specific modifications, the details thereof are not to be construed as limitations except to the extent indicated in the following claims.

What is claimed is:

1. A compound of the formula wherein R is alkyl of 1 to 4 carbons, inclusive.

2. Compound of claim 1 which is dimethylsulfonium-Z- (methoxycarbonyl carbonyl] phenacylide.

3. Dimethylsulfonium 2 [(ethoxycarbonyl)carbonyl]-4'-nitrophenacylide.

References Cited Ratts et al.: J. Org. Chem. 31, 1185-1188 (1966).

LORRAINE A. WEINBERGER, Primary Examiner J. F. TERAPANE, Assistant Examiner U.S. Cl. X.R.

, UNITED STATES PATENT OFFICE CERTHHQATEfHFQORREETMMJ Patent No. 3;739, Dated June 12, 197} Inventor(s) K nn h Wayne Rat ts It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1, in the section above the Abstract of the Disclosure, immediately following "65141" please insert assignor to Monsanto Company, St. Louis, Mo.

Column M; line 52, "liquid medium" should read liquid media Column 4, line 52, "such as tetrahydroufuran" should read such as tetrahydrofura Column line 33, "R R a, b, c and X as defined above" should read R R a, b, c and X are as defined above Column 6; line 17, the word "cellullosic" should read cellulosic Column 7, at line 5, reading "Diesel 011 glycols", please insert a comma as follows Diesel oil, glycols Column 7, at line 4, reading "include for ex-", please insert a comma as follows include, for ex- Signed and sealed this 2nd day of April 197A,

(SEAL) Attest:

EDWARD M,FLETCHER,JR. C. MARSHALL DANN Attesting Officer Commissioner of Patents FORM powso ($69) USCOMM-DC some-ps9 U.5l GOVERNMENT PRINTING OFFICE: I969 0-365-334 

